The present invention concerns fluid silico-acrylic compositions which are transparent, colourless and stable over time, and can be polymerised by heat or radiation, by a radical-type mechanism, with a very low water and volatile solvent content, the method of preparing them and their application to the obtaining of coatings resistant to abrasion and scratching.
Synthetic organic polymers and more particularly organic polymers transparent to sunlight, such as certain (meth)acrylic or terephthalic resins, are limited in their development by their low resistance to abrasion and their tendency to scratch. In order to obviate these drawbacks, it is often proposed to protect them with an anti-scratch and anti-abrasion coating which can be obtained by photopolymerisation of a film of a composition, aqueous or nonaqueous, containing particles of silica, one or more polymerisable acrylic monomers, in the presence of a photoinitiator and possibly one or more silanes. Amongst the latter compositions it is possible to cite amongst others those described in the patents U.S. Pat. Nos. 4,348,462, 4,455,205, 4,478,876, 4,486,504, 4,491,508, 4,822,828, 5,260,350 and 5,374,483.
EP-A-317.858 describes the preparation of compositions in a solvent medium containing a partial condensate of colloidal silica with a silane, at least 60% of which is of the vinylsilane type, a monomer of the multifunctional (meth)acrylate type, preferably soluble in water, and a lower alcanol, preferably isopropanol. It is this mixture in a solvent medium which is applied to synthetic films in order to obtain abrasion-resistant coatings. These compositions contain relatively high quantities of solvent, which it is necessary to evaporate during use.
U.S. Pat. No. 5,232,964 describes the preparation of a composition which forms a transparent coating which can be coloured and is resistant to abrasion after curing under radiation, comprising at least one multifunctional acrylate monomer, a silane, colloidal silica dispersed in a solvent plus a quaternary ammonium salt which gives the ability to be coloured.
JP-05-179.157 and JP-05-320.289 describe the preparation of abrasion-resistant compositions including colloidal silica, vinyltrimethoxysilane, and a mixture 1,6-hexanediol diacrylate and a di- or triacrylate isocyanurate. However, these compositions must necessarily be diluted with solvents in order to be used as a coating in a thin film.
Although the compositions described in these documents make it possible to obtain coatings having good performance both with regard to protection against abrasion and scratching and with regard to adhesion, at the present time compositions are also being sought which have further improved qualities notably with regard to fluidity, stability over time and environmental protection (reduction in volatile organic compounds or VOCs).
However, the applicant has discovered fluid compositions which are transparent, colourless and stable over time, and can be polymerised by heat or radiation, by a radical-type mechanism, with a high silica concentration, and a very low water and volatile solvent content, giving after polymerisation a coating which is hard and adherent and has good resistance to abrasion and scratching, meeting the above criteria.
The present invention concerns more precisely fluid silico-acrylic compositions, which can be polymerised by heat and radiation, by a radical-type mechanism, with very low water and volatile solvent content, containing silica, a silane and a multifunctional acrylic monomer, characterised by the fact that the silica is in the form of individualised particles, with a mean diameter of between 40 and 100 nm, not linked to each other by siloxane bonds, by the fact that the silane is a vinylsilane of formula (I)
H2Cxe2x95x90CHxe2x80x94Si(OR)3xe2x80x83xe2x80x83(I)
in which R represents a methyl or ethyl radical, and in that the multifunctional acrylic monomer is 1,6-hexanediol diacrylate, designated by the abbreviation HDDA, and by the fact that they are transparent, colourless and stable over time.
In the system of the present invention, the term polymerisable under radiation indicates that the coating can be cured under ultraviolet radiation in the presence of a photoinitiator or under electron beams without requiring a photoinitiator, and the term polymerisable by heat indicates that the coating can be cured by heat treatment in the presence of a radical catalyst.
The object of the invention is more particularly compositions as defined above, characterised in that they contain 5 to 60% by weight silica.
Amongst the latter compositions, the invention notably relates to compositions characterised in that they contain 30 to 50% by weight silica in the form of individualised particles, not linked to each other by siloxane bonds, and having a mean diameter of between 40 and 100 nm, preferentially approximately 50 nm.
Amongst the above compositions, there can be cited particularly those characterised by the fact that they contain 0.2 to 1.25 g of vinylsilane of formula (I), per gram of initial dry silica, preferentially between 0.3 and 0.65 g of vinylsilane of formula (I) per gram of initial dry silica.
The compositions according to the invention are stable over time; it is in fact found that, under optimum storage conditions, that is to say away from heat and light, at the end of several weeks to several months after the preparation of the product, there is still a clear, limpid, transparent and colourless solution. No sedimentation of the silica is noted, nor formation of gels from the silica or silanes. No appearance of haze is noted.
The compositions according to the invention are particularly fluid. Their Brookfield viscosity, after manufacture, determined at 20xc2x0 C. with a Brookfield RVT apparatus at 780 rev/min is low (less than 500 mPa.s), which makes it possible to use them as they are without subsequent dilution with solvents. It is particularly favourable from the point of view of reduction in volatile organic compounds (VOCs). They are also almost free of water and volatile solvents. They contain by weight less than 1% water.
Moreover, they have a very low volatile solvent content, preferably less than 6.5% by weight, notably less than 5%, particularly less than 3%, more particularly less than 2%.
The compositions according to the invention are miscible with organic solvents themselves miscible with HDDA. They can obviously be diluted with HDDA, so as to reduce, if desired, their silica concentration.
According to the invention, the compositions as defined above can be prepared by means of a method characterised in that there are mixed, at room temperature, under stirring, an aqueous sol of acid silica containing the required quantity and grade of silica, the chosen quantity of vinylsilane of formula (I), the required quantity of HDDA and isopropyl alcohol, referred to as IPA, so that the quantity of vinylsilane of formula (I) is between 0.2 g and 1.25 g per gram of initial dry silica, and preferably between 0.3 g and 0.65 g per gram of initial dry silica, and then this mixture is subjected to distillation under reduced pressure and under stirring, at a temperature below 50xc2x0 C., until the water and volatile solvents are eliminated in order to obtain a composition according to the invention.
The particles of silica, after elimination of the water and volatile solvents, lose their hydrophilic character and are thus dispersed in the HDDA. The stability of the composition according to the invention is surprising and particularly advantageous for their use.
This is because it is highly advantageous industrially to be able to obtain solvent-free compositions which remain stable over time. This aim has been achieved by regulating the quantity of vinylsilane of formula (I) according to the quantity of silica used.
The aqueous sol of acid silica is either available commercially or prepared extemporaneously by the treatment, according to known techniques, with an ion exchange resin in acid form, of an aqueous sol of commercial silica having a pH of 8 to 10.
These aqueous silica sols are available commercially and are notably sold by the applicants under the name KLEBOSOL(copyright).
The initial aqueous silica sols used in the invention contain up to 60% by weight silica, in the form of individualised particles, with a mean diameter of between 40 and 100 nm, not linked together by siloxane bonds and with a pH of between 1 and 3 and preferably approximately 2.
The vinylsilanes of formula (I) and HDDA are commercial products.
HDDA is notably sold by various companies: UCB/RADCURE (commercial name HDDA), CRAY VALLEY (SR 238), AKCROS (Actilane 425), HENKEL (Photomer 4017).
Vinyltrimethoxysilane and vinyltriethoxysilane are sold by SIVENTO respectively under the trade name Dynasylan VTMO and Dynasylan VTEO, and by WITCO respectively under the trade name SILQUESTA-171 and SILQUEST A-151.
The compositions according to the invention have interesting properties notably because of their high silica concentration, their fluidity and their stability over time. They can easily be deposited on different types of support, described previously, and cured by radical-type mechanisms by heat or radiation (UV or electron beam) resulting in the formation of a thin film having good adhesion to the support and good resistance to abrasion and scratching, which makes them particularly useful for the production of transparent colourless protective coatings.
This is why another object of the present invention is a method of protecting a synthetic organic polymer notably against scratching and abrasion, characterised in that a layer of an above composition is deposited on said polymer and then said composition is cured.
The compositions according to the invention have silica particles with a diameter of between 40 and 100 nm, and particularly 50 nm, and are therefore particularly advantageous for obtaining anti-scratch lacquers on transparent colourless plastic, such as optical glasses or transparent plastic materials which can be used in the building trade, or on other substrates (nontransparent plastic materials, glass, wood, metal).